Urea as an Energy Carrier

Report
Urea as an Energy Carrier
Paean or Pee-On?
Presentation by
Gilbert “Bert” Stunkard
NPRE 498 ES
November 29, 2010
Urea as an energy carrier
Urea as a hydrogen carrier
 Direct Urea fuel-cell
 Urea Production/Manufacture
 Urea: Vision, Economics, Advantages,
Disadvantages
 Direct Ammonia Fuel Cell

Urea properties
Source: en.wikipedia.org/wiki/urea1
Urea properties
Source: en.wikipedia.org/wiki/urea
Urea as a Hydrogen Carrier
0.33 M Urea, inexpensive Ni catalyst, electrochemical oxidation.
Claim this is the first technology that directly converts urea to
hydrogen.
Bryan K. Boggs, Rebecca L. King, Gerardine G. Botte* ,“Urea electrolysis: direct
hydrogen production from urine”, in Chem. Commun., 2009, 4859-4861. (Dept. of
Chemical and Biomolecular Engineering, Ohio University, Athens OH)2
Urea as a Hydrogen Carrier
CO2 is actually captured at potassium carbonate K2CO3.
OH- provided as potassium hydroxide (KOH).
Nitrogen at the anode, hydrogen at the cathode.
Urea as a Hydrogen Carrier

Explored Ni, Pt, Pt-Ir, Rh catalysts

Nickel oxyhyrdoxide modified nickel
electrodes (NOMH) electroplated on Ni
foil, Ni gauze, Ti Foil, Ti gauze yield higher
current densities than M/Ni (metallic
substrate) electrodes
Urea as a Hydrogen Carrier
Nickel in hydroxide media converts to
Ni(OH)2 (Ni2+) and NiOOH (Ni3+)
 Ionic nickel probably enhances
electrochemical oxidation


Absorption of urea on NiOOH surface
likely rate limiting step.
Urea as a Hydrogen Carrier
Requires electric energy to release
hydrogen
 1.4 [v] achieved experimentally (0.37 [v]
required theoretically) vs 2.0 [v] for
hydrogen
 Experimentally requires 30 % less energy
than electrolytic hydrogen (theoretically
could use 70% less)

Urea as a hydrogen carrier

Research project was to remediate urea
containing waste water from urea
manufacture or to use urine or biomass
produced urea as fuel
Direct Urea Fuel Cell
Rong Lan, Shanwen Tao*, and John T. S. Irvine, “A direct urea
fuel cell – power from fertiliser and waste”, in Energy.
Environ. Sci. 2010, 3, 438-441. (Herriot Watt University,
Edinburgh. University of St. Andrews, Fife, UK).3
Again, claim first time achievement
Direct Urea Fuel Cell
Direct Urea Fuel Cell
Theoretical open circuit voltage (OCV):
1.146 [v] at room temperature (H2/O2
fuel cell is 1.23 [v]).
 Theoretical maximum efficiency is 102.9%
at room temperature (vs 83 % for H2).
 Positive entropy change of reaction 3.
Absorbs heat from ambiance and
converts to electricity.

Direct Urea Fuel Cell –
Technical Challenges
Hydrolysis of urea produces ammonia.
Reaction of urea with oxygen produces
CO2.
 Not compatible with acidic Nafion
membrane and other proton exchange
membrane fuel cell (PEMFCs) mebranes.

Direct Urea Fuel Cell –
Technical Challenges
Alkaline membranes based on ammonia
quaternary salts are CO2 compatible and
introduction of CO2 at cathode can
improve performance, allowing use of wet
air.
 Amberlite IRA 78 Hydroxide, a styrenedivinyl benzene resin
 (R)n~N+(CH3)3 OH
Urea Fuel Cell – Tech Challenges
Divinylbenzene crosslinks make a 3-D network resin
Polystyrene graphic: http://en.wikipedia.org/wiki/Polystyrene
Quaternary ammonium hydroxide groups added by presenter
Direct Urea Fuel Cell –
Technical Challenges
AER: Membrane: Amberlite IRA78,
hydroxide form, 60/40 with (poly vinyl
alcohol) PVA MW 50,000.
 Current Collectors: Carbon papers
(Toray 090, water proofed for anode, plain
for cathode, E-TEK).
 Low cost catalyst like nickel, silver, MnO2
are stable in the alkaline membrane
environment

Direct Urea Fuel Cell –
Two different anodes

Pt/C (30 wt % , E-TEK 0.6 mg/cm2).

Ni/C (Nano size nickel mixed with carbon
50/50 wt %, ~20 mg/cm2).
Direct Urea Fuel Cell –
Three different cathodes

Pt/C (30 wt % , E-TEK 0.6 mg/cm2).

Ag/C (Nano size silver mixed with carbon
50/50 wt %, ~20 mg/cm2).

MnO2/C (Nano size MnO2 mixed with
carbon 20 wt % MnO2, ~20 mg/cm2).
Direct Urea Fuel Cell –
Three grades urea
ACS grade, various concentrations
 Commercial Ad-Blue (32.5 wt % urea)
from a local garage.
 Human urine (source not revealed)

Direct Urea Fuel Cell
Ni/C – MnO2/C Fuel cell performance, room temperature (O2)
Direct Urea Fuel Cell
Ni/C – MnO2/C Fuel cell performance, 50o C, O2
Direct Urea Fuel Cell –
Performance Issues
Higher urea concentrations (3,5 M)
decreased voltage.
 Urea molecules are large: high
concentration may cause slow diffusion at
the anode thus increasing polarization
loss.
 Elevated temperature benefits all anode
and cathode types.

Direct Urea Fuel Cell –
Performance Issues

Ni/C Anode, MnO2 cathode: slightly
higher voltage and power density than
Ag/C cathode.

At 50o C, Ni/C, MnO2 (using O2) cell
outperformed all Pt/C cell at room
temperature (using air).
Direct Urea Fuel Cell –
Performance of Ad-Blue
AdBlue (32.5%, ~5 M) ironically had
higher voltages and power densities than
comparable urea solutions (0.3 mW/cm2
versus 0.2 mW/cm2)
 Dilute Ad-blue gave better performance
than pure Ad-Blue.
 10% Ad-Blue highest current and power
densities

Direct Urea Fuel Cell

Research project was to remediate urea
containing waste water from urea
manufacture or to use urine or biomass
produced urea as fuel
Urea – Manufacture4

Basaroff reactions:
NH2COONH4: ammonium carbamate
 Requires ammonia
 Ammonia requires hydrogen

Urea – Manufacture4

Basaroff reactions:

Step 2 is the dehydration of ammonium
carbamate to urea at increased
temperature and pressure
Urea Manufacture4
Hydrogen plant, ammonia plant, urea plant
usually integrated on a single site
 Hydrogen plant usually employs steam
reformation of methane
 Carbon dioxide goes to urea plant
 Hydrogen goes to ammonia plant, where
nitrogen and hydrogen are reacted over
iron catalysts (Haber process)

Urea Manufacture4
Integrated plant optimizes energy transfer
and waste recycle
 Incomplete utilization of ammonia and
carbon dioxide on each pass requires
stripping of product from reactants and
recycle of reactants
 Wastewater is high in urea (~2%),
chemical hydrolysis returns ammonia and
carbon dioxide to reactor

Urea – Manufacture4
Urea – Manufacture4
Carbamate solution is corrosive
(carbamate is an electrolyte)
 Urea is not corrosive
 Heat exchange critical to process
efficiency
 Carbamate solutions are most destructive
to heat exchangers

Urea Vision
Urea less toxic than ammonia or
methanol
 Urea less combustible, less explosive than
hydrogen, ammonia, or methanol
 Urea easier to transport than anhydrous
ammonia or hydrogen

Urea Vision
Green hydrogen + waste carbon dioxide
= urea
 Initiate distribution via existing
agricultural and Ad-blue© suppliers
 Ad-Blue: a 32.5% solution of urea and
deionized water used for nitrogen oxides
removal from diesel exhaust5

Urea Vision5
Source: BP/Dureal “Guide to Ad-Blue”, 2010
Urea Vision
Agricultural urea granules are treated
with formaldehyde4
 Urea prills have problems with dust and
moisture absorption4
 Ad-Blue freezes at -11o C (12o F)5
 Urea solutions slowly decompose to
ammonia and isocyanuric acid.4

Urea: Energy density comparison
Urea – Cost Comparison
Substance
Pricet
( ¢/kg)
Methanol
Liquid NH3
Urea
44.5
45.0
38.0
Gravimetric
Energy
Density*
(MJ/kg)
22.66
22.48
10.536
Energy
Cost
(¢/MJ)
1.96
2.00
3.61
Gravimetric
Energy
Density
(kW.hr/kg)
6.278
6.244
2.9267
October prices from www.icis.com, prices at plant
*Calculated from heats of combustion found in CRC Handbook Online
t
Energy
Cost
(¢/kW.hr)
7.07
7.21
13.0
Urea Economics
Conversion of natural gas to urea => 55%
energy efficiency. 3
 Efficiency of fuel cell yet to be
determined, optimized, or perfected
 With 50% fuel-cell efficiency, overall
efficiency would be ~25%.
 Comparable to LNG fired internal
combustion engine.

Urea Economics
Urea must become comparable in price
(based on MJ/kg) to methanol or
ammonia.
 Urea fuel-cell efficiency would need to
exceed methanol or ammonia fuel cell
efficiency
 Otherwise confined to niches where
flammability of methanol or toxicity of
ammonia present problems.

Ammonia as energy carrier
No need to make urea
 CO2 can be sequestered at hydrogen
plant
 Carbon neutral: green hydrogen +
atmospheric nitrogen = ammonia
 Ammonia fuel cells have head start. First
direct ammonia fuel cell was 1969.6
 Potential to make ammonia
electrolytically from just water and
nitrogen.

Ammonia Fuel Cell
Rong Lan and Shanwen Tao*, “Direct Ammonia Alkaline Anion-Exchange Membrane Fuel Cells”, in Electrochemical and Solid-State
.
Letters, 13(8) B83-B86 (2010). Heriot-Watt University, Edingburgh, UK, Department of Chemistry 6
Ammonia Fuel Cell
Ammonia Fuel Cell - Membrane

Membrane: Chloroacetyl poly(2,6dimethyl-1,4-phenylene oxide) (CPPO)
blended 50/50 with Polyvinyl alcohol
(PVA) 50K M.W. for strength.

S
Structures: SCIFINDER/CAS Chemical Substance Registry, RN 24938-67-8, RN 79-04-8
Ammonia Fuel Cell - Electrodes
Anode: Cr-decorated Ni (CDN) molar
ratio 97.7:2.3 Ni/Cr. 50/50 wt %
CDN/Carbon, 10 mg/cm2.
 Cathode: MnO2/C (20 wt % MnO2)
cathode, 20 mg/cm2.
 Also tested PtRu/C anode with Amberlite
IRA400/PVA membrane

Ammonia Fuel Cell
Reference: 6
Ammonia Fuel Cell
Claim maximum power density of 16
mW/cm2 with CPPO membrane at
voltage of ~0.85 [v] using pure oxygen.6
(Some conflict with plot in previous slide).
 1.17 [v] is theoretical maximum

Urea as hydrogen carrier2
Hydrogen carrier – requires electricity to
free hydrogen from urea
 Experimental cell only uses 30 % less
energy than freeing hydrogen from water
 Theoretically limited to 70% less energy
than freeing hydrogen from water
 Process development is for remediation
of urea production wastewater or urine
as fuel

Urea Fuel Cell
Urea less toxic than ammonia, less
flammable than methanol
 Urea likely more expensive fuel than
ammonia or methanol
 Urea is not carbon neutral
 Urea requires ammonia to make,
ammonia requires hydrogen

Further research
Urea fuel cell improvement for use with
urea waste or biomass derived urea
 Ammonia more promising than urea as
energy carrier
 Ammonia fuel cell improvement
 Possible electrolytic production of
ammonia from water and atmospheric
nitrogen

References
(1) “Urea”, http://en.wikipedia.org/wiki/Urea
 (2) Bryan K. Boggs, Rebecca L. King, Gerardine G.
Botte* ,“Urea electrolysis: direct hydrogen
production from urine”, in Chem. Commun., 2009,
4859-4861. (Dept. of Chemical and Biomolecular
Engineering, Ohio University, Athens OH)
 (3) Rong Lan, Shanwen Tao*, and John T. S. Irvine,
“A direct urea fuel cell – power from fertiliser
and waste”, in Energy. Environ. Sci. 2010, 3, 438441. (Herriot Watt University, Edinburgh.
University of St. Andrews, Fife, UK).

References



(4) Josef H. Meesen, “Urea”, in Ullman’s
Encyclopedia of Industrial Chemistry, 2010,
Wiley-VCH Verlag & Co. KGaA, Weinheim,
10.1002/ 14356007.a27_333.pub2.
(5) BP and Dureal “Ab-Blue Handbook”,
2010
(6) Rong Lan and Shanwen Tao*, “Direct
Ammonia Alkaline Anion-Exchange
Membrane Fuel Cells”, in Electrochemical and
Solid-State Letters, 13(8) B83-B86 (2010).
Heriot-Watt University, Edingburgh, UK,
Department of Chemistry.
Additional references



Hazel Muir, “Pee Power”, in New Scientist,
207(2774), 21 August, 2010, 27-39.
Dr. Carl Feickert, “Hydrogen production
from waste stream urea recover”, ERDCCERL, Champaign, IL Branch.
George Marnellos and Michael Stoukides,
“Ammonia synthesis at atmospheric
pressure”, in Science, 282, 1998, 98-100.
Covers electrolytic ammonia preparation at
atmospheric pressure and room
temperature via hydrogen and nitrogen.

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